CN104557749B - 3-phenyl-5-(4-trifluoromethyl phenylamino)-4H-1,2,4-triazole as well as synthetic process and application thereof - Google Patents

3-phenyl-5-(4-trifluoromethyl phenylamino)-4H-1,2,4-triazole as well as synthetic process and application thereof Download PDF

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CN104557749B
CN104557749B CN201410803491.3A CN201410803491A CN104557749B CN 104557749 B CN104557749 B CN 104557749B CN 201410803491 A CN201410803491 A CN 201410803491A CN 104557749 B CN104557749 B CN 104557749B
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phenyl
triazole
trifluoromethyl
benzoyl
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CN104557749A (en
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巨修练
乔恒
余勇
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Nanxiong Huixing Chemical Technology Co.,Ltd.
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Wuhan Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/14—Nitrogen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

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  • Organic Chemistry (AREA)
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  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
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Abstract

The invention relates to 3-phenyl-5-(4-trifluoromethyl phenylamino)-4H-1,2,4-triazole as well as a synthetic process and an application thereof. A synthetic process of 3-phenyl-5-(4-trifluoromethyl phenylamino)-4H-1,2,4-triazole comprises the following steps: 1) carrying out reaction on benzoyl chloride which is taken as a raw material and potassium thiocyanate to generate benzoyl isothiocyanate; 2) carrying out reaction on benzoyl isothiocyanate and p-trifluoromethyl phenylamine to produce an intermediate 1-benzoyl-3-(4-trifluoromethyl phenylamino) thiourea; and 3) carrying out reaction on the intermediate 1-benzoyl-3-(4-trifluoromethyl phenylamino) thiourea and hydrazine hydrate to produce a target product 3-phenyl-5-(4-trifluoromethyl phenylamino)-4H-1,2,4-triazole. The 3-phenyl-5-(4-trifluoromethyl phenylamino)-4H-1,2,4-triazole has the beneficial effects that a new compound is determined by adopting a spray method when concentration of a target compound is 200ppm, the efficiency of protecting malt in 24 hours is 60%, the efficiency of protecting malt in 48 hours is 70%, and the 3-phenyl-5-(4-trifluoromethyl phenylamino)-4H-1,2,4-triazole has a potential of being further developed into an insecticide.

Description

3- phenyl -5- (4- trifluoromethylbenzene amido) -4h-1,2,4- triazole and its synthesis Technique and application
Technical field
The present invention relates to triazole class compounds, specifically 3- phenyl -5- (4- trifluoromethylbenzene amido) -4h-1,2,4- tri- Nitrogen azoles and its synthesis technique and application.
Technical background
Triazole class compounds have extensive physiologically active, 20 century 70s, and the efficient sterilizing of triazole class compounds is lived Property cause international pesticide circle great attention it has been found that the substituted radical on n- methyl carbon can widely be taken by other groups Dai Erqi biological activity keeps constant or increases.By the conversion of substituted radical, (e.g., phenyl can be by five yuan or hexa-atomic miscellaneous Ring, all types of saturations or undersaturated alkyl, ester, Tong Deng functional group or bridge benzyl are replaced), synthesize and filter out a collection of tool There are the triazole class compounds of bactericidal activity.Including the very high triazolyl-o of activity, n- acetal compound.Opened later again Systemic fungicide triazolone, Triadimenol etc. are sent out.So far, the systemic fungicide of exploitation mainly has triazole type, benzene And imidazoles, miazines, imidazoles, morpholine class etc., most important of which systemic fungicide is triazole class compounds.But killing Although there being the compound containing triazole ring to use as insecticide in worm agent research, but framing structure is not triazole ring.
Content of the invention
The technical problem to be solved is to propose a kind of noval chemical compound 3- phenyl -5- for above-mentioned prior art (4- trifluoromethylbenzene amido) -4h-1,2,4- triazole and its synthesis technique and application.
Present invention solution above-mentioned technical problem the technical scheme is that 3- phenyl -5- (4- trifluoromethylbenzene amido) - 4h-1,2,4- triazoles, its structural formula is:
The technical scheme of preparation method of the present invention is: 3- phenyl -5- (4- trifluoromethylbenzene amido) -4h-1,2,4- three nitrogen The synthesis technique of azoles, includes following steps:
1) with Benzenecarbonyl chloride. (1) for raw material through reacting generation benzoyl isothiocyanate (2) with potassium rhodanate；
2) itself and p-trifluoromethylaniline are reacted production intermediate 1- benzoyl -3- (4- trifluoromethyl) thiourea (3)；
3) by this intermediate and hydration hydrazine reaction productive target product 3- phenyl -5- (4- trifluoromethylbenzene amido) -4h-1, 2,4- triazoles (4), wherein 1- benzoyl -3- (4- trifluoromethyl) thiourea according to the molar ratio: hydrazine hydrate=1:4～8, Its reaction equation is:
Step 1) solvent that reacts is acetonitrile, acetone or oxolane.
Step 2) react for back flow reaction, response time 5～12h.
The beneficial effects of the present invention is: novel compound of present invention under target compound 200ppm concentration, through spraying Method measures, 24 hours preventing and treating Fructus Hordei Germinatus effects 60%, and 48 hours prevention effects 70% have and are further developed as the latent of insecticide Power.
Specific embodiment
For further understanding the present invention, with reference to instantiation, the present invention is elaborated.
Embodiment 1
The preparation of intermediate benzoyl isothiocyanate (3)
Add potassium thiocyanate 2.10g (21.6mmol) in 100ml there-necked flask, add acetone 60ml dissolving.It is warmed up to 45 ～50 DEG C, be slowly added dropwise the mixed solution of Benzenecarbonyl chloride. 2.1ml (18mmol) and 20ml acetone, completion of dropping continue reaction 3～ 4h.It is as cold as room temperature.Sucking filtration, with washing with acetone, collects filtrate and can be directly used for lower step.By 2.9g (18mmol) to trifluoromethylbenzene Amine is dissolved in 20ml acetone, and is added drop-wise in 30min in benzoyl isothiocyanate (2), temperature rising reflux reaction 8～ 9h.Tlc follows the tracks of.Reaction is finished, solvent evaporated, with frozen water dilution, collected by suction solid after stirring, obtains 1- with ethyl alcohol recrystallization Benzoyl -3- (4- trifluoromethyl) thiourea (3), white needle-like crystals 1.20g, total recovery 20.5%.
The preparation of target product 3- phenyl -5- (4- trifluoromethylbenzene amido) -4h-1,2,4- triazole (4)
1- benzoyl -3- (4- trifluoromethyl) thiourea (3) 1.0g (3mmol), second is added in 100ml there-necked flask Alcohol 30ml and appropriate acetic anhydride.Heating makes solid entirely molten, and the ethanol solution of the hydrazine hydrate (12mmol) by 80% is added drop-wise to above-mentioned In solution.Back flow reaction.Tlc follows the tracks of.Reaction is finished, and standing cooling has white solid to separate out.Sucking filtration, collects solid dehydrated alcohol It is recrystallized to give target compound 3- phenyl -5- (4- trifluoromethylbenzene amido) -4h-1,2,4- triazole (4) 0.3g, yield 37%, 260 DEG C of decomposition.1H nmr (dmso-d6,300mhz) δ: 7.78～7.80 (m, 4h, phh-cf3), 7.95～7.97 (m, 3h, phh-triazole), 8.17～8.20 (m, 2h, phh-triazole), 10.03 (s, 1h, triazoleh)；ms m/z (%): 304 (m+,10),145(16),104(34),77(36),69(100).
Embodiment 2
The preparation of intermediate benzoyl isothiocyanate (3)
Add potassium thiocyanate 2.10g (21.6mmol) in 100ml there-necked flask, add acetone 60ml dissolving.It is warmed up to 45 ～50 DEG C, be slowly added dropwise the mixed solution of Benzenecarbonyl chloride. 2.1ml (18mmol) and 20ml acetone, completion of dropping continue reaction 3～ 4h.It is as cold as room temperature.Sucking filtration, with washing with acetone, collects filtrate and can be directly used for lower step.By 6.0g (36mmol) to trifluoromethylbenzene Amine is dissolved in 20ml acetone, and is added drop-wise in 30min in benzoyl isothiocyanate (2), and temperature rising reflux reacts 12h. Tlc follows the tracks of.Reaction is finished, solvent evaporated, with frozen water dilution, collected by suction solid after stirring, obtains 1- benzene with ethyl alcohol recrystallization Formoxyl -3- (4- trifluoromethyl) thiourea (3), white needle-like crystals 1.0g, total recovery 18%.
The preparation of target product 3- phenyl -5- (4- trifluoromethylbenzene amido) -4h-1,2,4- triazole (4)
Add 1- benzoyl -3- (4- trifluoromethyl) thiourea (3) 5.0g (15mmol) in 500ml there-necked flask, Ethanol 100ml and acetic anhydride 10ml.Heating makes solid entirely molten, and the ethanol solution of the hydrazine hydrate (60mmol) by 80% is added drop-wise to above-mentioned In solution.Back flow reaction.Tlc follows the tracks of.Reaction is finished, and standing cooling has white solid to separate out.Sucking filtration, collects solid dehydrated alcohol It is recrystallized to give target compound 3- phenyl -5- (4- trifluoromethylbenzene amido) -4h-1,2,4- triazole (4) 1.3g, yield 30%.
Embodiment 3
Preparing of intermediate benzoyl isothiocyanate (3) is same as Example 1.
1- benzoyl -3- (4- trifluoromethyl) thiourea (3) 3.0g (9mmol), second is added in 100ml there-necked flask Alcohol 50ml and 5ml acetic anhydride.Heating makes solid entirely molten, and the ethanol solution of the hydrazine hydrate (46mmol) by 80% is added drop-wise to above-mentioned solution In.Back flow reaction 10 hours.Reaction is finished, and standing cooling has white solid to separate out.Sucking filtration, collects solid dehydrated alcohol recrystallization Obtain target compound 3- phenyl -5- (4- trifluoromethylbenzene amido) -4h-1,2,4- triazole (4) 0.8g, yield 29%.
Embodiment 4
Preparing of intermediate benzoyl isothiocyanate (3) is same as Example 1.
Add 1- benzoyl -3- (4- trifluoromethyl) thiourea (3) 6.0g (18mmol) in 250ml there-necked flask, Ethanol 100ml and 15ml acetic anhydride.Heating makes solid entirely molten, and the ethanol solution of the hydrazine hydrate (90mmol) by 80% is added drop-wise to above-mentioned In solution.Back flow reaction 8 hours.Reaction is finished, and standing cooling has white solid to separate out.Sucking filtration, collects solid dehydrated alcohol weight Crystallization obtains target compound 3- phenyl -5- (4- trifluoromethylbenzene amido) -4h-1,2,4- triazole (4) 1.7g, yield 30%.
Embodiment 5
Testing compound 3- phenyl -5- (4- trifluoromethylbenzene the amido) -4h-1,2,4- triazole that embodiment 1 is obtained It is made into 1000ppm with acetone, then dilute with water is that 200ppm is carried out to the culture Semen Tritici aestivi (10 plants/nursery pipe) of 6 days in greenhouse Spraying treatment.After medicinal liquid air-dries, nursery pipe is put in seedling culture frame, and seedling culture frame is immersed in the water.Silk screen is placed on wheat seedling prop up Frame, is placed on gauze the wheat leaf blade for cultivating wheat aphid, carries out connecing worm process, so that wheat aphid is uniformly moved to little Mai Shang.After 24 hours, Coarse Mesh Gauze is taken away, wheat plant is transferred on Caulis et Folium Tritici aestivi, between Semen Tritici aestivi nursery pipe, have enough skies Between, seedling culture frame has water, so that aphid can not be shifted between nursery pipe.Caulis et Folium Tritici aestivi, in warm indoor cultivation 5 days, checks that each processes Semen Tritici aestivi Aphed population on Seedling, calculates prevention effect.24 hours prevention effects 60%, 48 hours prevention effects 70%.
The compound of the present invention, 3- phenyl -5- (4- trifluoromethylbenzene amido) -4h-1,2,4- triazoles have preferably Insecticidal activity, has the potentiality being further developed as insecticide.

Claims (3)

1.3- phenyl -5- (4- trifluoromethylbenzene amido) -4h-1,2,4- triazoles, its structural formula is:
.
2.3- phenyl -5- (4- trifluoromethylbenzene amido) -4h-1, the synthesis technique of 2,4- triazoles, include following steps:
1) with Benzenecarbonyl chloride. (1) for raw material through reacting generation benzoyl isothiocyanate (2), the solvent of reaction with potassium rhodanate For acetonitrile, acetone or oxolane；
2) itself and p-trifluoromethylaniline are reacted production intermediate 1- benzoyl -3- (4- trifluoromethyl) thiourea (3), React for back flow reaction, response time 5 ~ 12 h；
3) by this intermediate and hydration hydrazine reaction productive target product 3- phenyl -5- (4- trifluoromethylbenzene amido) -4h-1,2, 4- triazole (4), wherein 1- benzoyl -3- (4- trifluoromethyl) thiourea according to the molar ratio: hydrazine hydrate=1:4 ~ 8, its Reaction equation is:
.
3. the 3- phenyl -5- described in claim 1 (4- trifluoromethylbenzene amido) -4h-1,2,4- triazole is as insecticide Application.
CN201410803491.3A 2014-12-19 2014-12-19 3-phenyl-5-(4-trifluoromethyl phenylamino)-4H-1,2,4-triazole as well as synthetic process and application thereof Active CN104557749B (en)

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